Monophosphorus Ligands And Their Use In Cross-Coupling Reactions
a monophosphorus ligand and cross-coupling reaction technology, applied in the field of pchiral monophosphorus ligands, can solve the problems of suzuki-miyaura coupling of sterically hindered substrates and further decrease of catalyst loading, and achieve the effect of reducing the catalyst loading and reducing the coupling speed
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example 1
(S)-3-tert-butyl-2,3-dihydrobenzo[d][1,3]oxaphosphol-4-yl trifluoromethanesulfonate oxide
[0043]
[0044]To a solution of (S)-3-tert-butyl-2,3-dihydrobenzo[d][1,3]oxaphosphol oxide -4-ol (50 mg, 0.221 mmol) and triethylamine (89 mg, 0.88 mmol, 4 equiv) in CH2Cl2 (2 mL) at 0° C. was added Tf2NPh (96 mg, 0.27 mmol, 1.2 equiv) over 1 min The mixture was stirred at rt for 2 h and then quenched with addition of water (2 mL). The CH2Cl2 layer was separated, dried over sodium sulfate, concentrated, and purified by silica gel column chromatography (eluents: hexanes to EtOAc) to provide (S)-3-tert-butyl-2,3-dihydrobenzo[d][1,3]oxaphosphol-4-yl trifluoromethanesulfonate oxide (75 mg, 0.21 mmol, 95%) as white solid. 1HNMR (500 MHz, CD2Cl2) g 7.58 (t, J=8.3 Hz, 1H), 7.03 (dd, J=8.2, 3.5 Hz, 1H), 7.00 (dd, J=8.5, 2.4 Hz, 1H), 4.67 (dd, J=14.2, 2.1 Hz, 1H), 4.46 (dd, J=14.1, 11.1 Hz, 1H), 1.21 (d, J=16.8 Hz, 9H); 31PNMR (202 MHz, CD2Cl2) δ 75.6; 13CNMR (125 MHz, CD2Cl2) δ167.1 (d, J=16.8 Hz), 150.0, ...
example 2
(S)-3-tert-butyl-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]oxaphosphole oxide by Suzuki Coupling with S-phos as the Ligand
[0045]To a solution of (S)-3-tert-butyl-2,3-dihydrobenzo[d][1,3]oxaphosphol-4-yl trifluoromethanesulfonate oxide (5 g, 13 9 mmol) and 2,6-dimethoxyphenylboronic acid (3.8 g, 20.9 mmol, 1.5 equiv), Pd2dba3 (383 mg, 0.42 mmol, 3 mol %), S-Phos (1.15 g, 2.79 mmol, 20 mol %) and KF (3.24 g, 55.8 mmol, 4 equiv) was charged degassed dioxane (30 mL). The mixture was stirred under nitrogen at 100° C. for 12 h. The mixture was cooled to rt and concentrated. To the residue was added DCM (30 mL) and 2 N NaOH (30 mL). The DCM layer was further washed with 2 N NaOH (30 mL) and brine (30 mL), dried over sodium sulfate, and concentrated. The residue was purified by column chromatography (hexane to EtOAc / MeOH 2 / 1) to provide the desired product as yellow solid (3 g, 8.66 mmol, 62%).1HNMR (500 MHz, CDCl3): δ=7.46 (t, J=7.9 Hz, 1H), 7.28 (t, J=8.4 Hz, 1H), 6.89 (m, 2H), 6.64...
example 3
(S)-3-tert-butyl-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]oxaphosphole oxide by Suzuki coupling with (R)-3-tert-butyl-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]oxaphosphole as the ligand
[0046]
[0047]To a mixture of (S)-3-tert-butyl-2,3-dihydrobenzo[d][1,3]oxaphosphol-4-yl rifluoromethanesulfonate oxide (215 g, 600 mmol) and 2,6-dimethoxyphenylboronic acid (164 g, 900 mmol, 1.5 equiv), Pd2dba3 (6.9 g, 7.5 mmol, 0.0125 equiv), (R)-3-tert-butyl-4-(2,6-dimethoxyphenyl)-2,3-dihydrobenzo[d][1,3]oxaphosphole (5.9 g, 18 mmol, 0.03 equiv) and KF (139 g, 2.4 mol, 4 equiv) was charged degassed dioxane (2 L). The mixture was stirred under nitrogen at 100° C. for 3 h, then cooled to rt and concentrated to remove most dioxane. To the residue was added DCM (1000 mL) and 2 N NaOH (500 mL). The DCM layer was further washed with 2 N NaOH (500 mL) and brine (500 mL), dried over sodium sulfate, and concentrated. The residue was purified by column chromatography (eluent: hexane to EtOAc / MeOH...
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